Perfume compositions containing substituted cyclohexane compounds

ABSTRACT

1. A PERFUME COMPOSITION COMPRISING A FRAGNANCE IMPARTING AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE FORMULAS   1,1-DI(H3C-),3-(H3C-CH(-O-R)-)-CYCLOHEXANE AND   1,1-DI(H3C-),3-(H3C-CO-)-CYCLOHEXANE   WHERE R IS AN ACYL GROUP CONTAINING NO MORE THAN 4 CARBON ATOMS AS AN ACTIVE FRAGANCE INGREDIENT AND AN AUXILLARY PERFUME ADJUVANT.

United States Patent Office 3,847,975 Patented Nov. 12, 1974 US. Cl.252-522 5 Claims ABSTRACT OF THE DISCLOSURE The use of certain novela,3,3-trimethyl cyclohexane methanol and esters thereof as fragranceingredients.

This application is a continuation-in-part of application Ser. No.862,023, filed Sept. 29, 1969, now abandoned, which is a division ofapplication Ser. No. 573,882, filed Aug. 22, 1966, now US. Pat.3,487,102.

This invention relates to the synthesis of a new alcohol and derivativesthereof, and a process for producing same.

I have found in accordance with my invention a number of new compoundsrepresented by the formulae and CH-CH:

I. II.

-- C -CH:

where R is H or an acyl group containing no more than 4 carbon atoms.These compounds are formed in accordance with my invention by treatingdihydromyrcene (3,7- dimethyl-l,6-octadiene) with formic acid alone orwith a lower carboxylic acid or water in the presence of an acidcatalyst, such as sulfuric acid, phosphoric acid, polyphosphoric acid, aLewis acid, or a sulfonic acid resin. An unexpected rearrangement occursto yield new compounds, namely esters of a,3,3-trimcthyl cyclohexanemethanol and the alcohol itself.

Compound II above is formed by oxidation of the alcohol u,3,3-trimethylcyclohexane methanol.

The alcohol and its esters, as well as the ketone, have pleasant odorswhich are of value as perfumes.

In carrying out the above process for producing compound 1 where wateris present, more or less alcohol is formed. The course of the reactionis shown as follows:

+ RCOOH err-cu.

Any water present can either form the alcohol directly or can hydrolyzethe ester formed to produce quantities of the corresponding alcohol.

Although the reaction may be performed in aqueous solution, higherconversions are obtained in refluxing formic acid or by the use of thecatalysts mentioned above in formic or other carboxylic acids.

The temperature will depend on the activity and amount of the catalyst.With a very active catalyst such as BF a temperature of C. gives a goodconversion in three hours using formic acid (90%) containing 15% BFetherate complex. Without a catalyst a fair conversion to the ester isobtained with refluxing formic acid (100 C.) in about ten hours. Thetime will vary inversely with the temperature. Therefore, ranges of timeand temperature will differ for each catalyst and with the amount ofcatalyst. In general, a temperature range of 35100 C. may be specifiedwith a preference of about 50-80 C. and time range of 1-15 hours. Atlower than optimum temperatures a mixture of the cyclic ester and theester of dihydro myrcenol is obtained. For example, at 25 C. withpolyphosphoric acid as catalyst in formic acid, the product containeddihydro myrcenyl formate as the major constituent. However, at 75-80with polyphosphoric acid, the cyclic material was obtained with only atrace of dihydro myrcenyl formate being present. Stannic chloride at.50C. yielded about a 50/50 mixture of dihydro myrcenyl formate and thecyclic ester in twelve hours.

.Neither the amount of catalyst nor the ratio of reactants is criticaland may vary over a wide range. When a carboxylic acid other than formicacid is used, a catalyst is required. The carboxylic acids maybe eitheranhydrous or contain varying amounts of water. The alcohol a,3,3trimethyl cyclohexane methanol was identified from the following data:

Microns: Assignment 3.0 Q. 0H. 7.2, 7.6 Gem dimethyl. 9.35 Secondary OH.

(Nuclear magnetic resonance) The NMR/ spectrum was in accordance withthe structure given below (I):

(EH-CH5 OH Proton A- (p.p.m.) Assignment count 3.4 (diffuse quartet) 1.1

H- l-OH trum of the ketone indicated a molecular weightof 154. The IRspectrum has the following absorptions:

C-CH; II

Microns Assignment 5.84 Carbonyl. 7.40 Q1300. 7.21, 7.26 Gem dimethyl.

The NMR spectrum was in accord with structure II. I

The a,3,3-trimethyl cyclohexane methanol, esters and ketone of thisinvention are useful fragrance ingredients. They can be used tocontribute a woody, minty, floral aroma nuance to perfume compositions.The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones, esters,and frequently hydrocarbons which are admixed so that the combined odorsof the individual components produce a pleasant or desired fragrance.

The perfume composition can also contain other auxiliary perfumeingredients such as olfactory materials, vehicles such as alcohol,glycol, or the like, or absorbent, or carriers such as absorbent solidslike material and synthetic gum, or encapsulating ingredients.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the compounds of this invention can be used to alter the aromacharacteristic of a perfume composition, for example, by highlighting,moderating or adding a top-note to other ingredients in the composition.

The amount of a,3,3-trimethyl cyclohexane compound used in perfumecompositions will depend on a variety of factors, including the otheringredients employed, their amounts and the effects which are desired.Perfume compositions containing as little as 2% by weight of .the

that these examples are illustrative and the invention is not to beconsidered as restricted thereto, except as indicated in the appendedclaims.

EXAMPLE I To a stirred mixture of 422 g. of dihydromyrcene (94%) and 307g. of 90% formic acid was added 44 g. of 'BF -etherate over a period often minutes. The mixture was stirred at 50 C. for four hours. The heatwas then removed and stirring continued for another thirty minutes. Anequal volume of water was added and the oil layer separated. The oillayer contained the formats ester. The water layer was extracted withbenzene and the combined organic layers washed neutral. After thesolvent was stripped off, the residue weight 490 g. and tested 66.6% asthe formate ester. Fractionation yielded a,3,3-trimethyl cyclohexanemethyl formate.

B.P. 70 C./3 mm.

Said formate had a woody, minty, rosy odor. It is represented by theformula:

compound of this invention, or even less, can be used to impart a mintyand/or piney odor to soaps, detergents, cosmetics and other products.The amount employed can range up to 15% or higher and will depend onconsidera-. tions of cost, nature of the end product, the/effect desiredon the particular product and the particular fragrance sought. In aperfume composition the a,3,3-trimethyl cyclohexane compound canrepresent from about 5 to 75% of the total composition by weight.

The u,3,3-trimethyl cyclohexane compound can be used alone or in aperfume composition as an olfactory component in detergents and soaps;space deodorants; perfumes; colognes; bath preparations such as bathoil, bath salts; hair preparations such as lacquers, brilliantines,pomades, and shampoos; cosmetic preparations such as creams, deodorants,hand lotions, sun screens; powders such as talc, dusting powders, facepowder and the like. When used as an olfactory component of a perfumedcomposition as little as 0.05% of the novel u,3,3-trimethyl cyclohexanecompounds will suflice to impart a piney or minty odor.

The following are examples of the manner in which I now prefer topractice the invention. It is to be understood The crude ester (500 g.)prepared as in Example I, was refluxed with a solution of 500 g. ofmethanol, 200 g. of sodium hydroxide 50%, and 58 g. of water for 1.5hours. Another 100 g. of water was added to the reaction mixture and themethanol was stripped off to 90 C. at atmospheric pressure. The residuewas washed with water, 1% acetic acid and water. The dried residueweighed 355 g. and tested 76% as the alcohol. Fractionation yieldeda,3,3-trimethyl cyclohexane methanol.

B.P. 100 C./10 mm. n 1.4618. D 0.9071.

g The product had a sweet, pungent, minty, camphoraceous odor. It isrepresented by the formula:

onorn EXAMPLE III A mixture of 800 g. of dihydromyrcene and 460 g. offormic acid (99%) was refluxed for 6 hours. After cooling, the mixturewas separated. The upper layer was rushed-over without washing to yield670 g. of acid free product testing 53.8% as a,3,3-trimethyl cyclohexanemethyl formate.

EXAMPLE IV RP 81 C./4.6- mm. n 1.4475. D 0.9315.

The product had a sweet, woody, floral odor. It is represented by theformula:

CHI-CH3 o-o-cH.

EXAMPLE V To 520 g. of a,3,3-trimethyl cyclohexane methanol was added asolution of 400 g. of chromic acid, 400 g. of acetic acid and 400 g. ofwater at 25-30 C. over a period of one hour. The reaction mixture wasstirred for another three hours at 30 C. The mixture was then dilutedwith 600 cc. of water and steam distilled. There was obtained 459 g. ofoil testing 96.5% as the ketone by oximation. Fractionation yielded3,3-dimethyl cyclohexyl methyl ketone.

B.P. 89 C./14 mm. 11 1.4530. D 0.8996. MP. of semicarbazone 191 C.

The product has a strong, minty, herbaceous odor. It is represented bythe formula:

EXAMPLE VI A mixture of 200 g. of dihydromyrcene, 200 g. of 80% aceticacid and 20 g. concentrated sulfuric acid was refluxed for 5.5 hours.The aqueous layer was separated and 75 cC. of benzene was added to thetop layer which was washed twice with water and the solvent strippedoff. The residue weight 185 g. and tested 61% a,3,3-trimethylcyclohexane methyl acetate.

EXAMPLE VII EXAMPLE VIII A mixture of 300 g. of dihydromyrcene, 200 g.of isobutyric acid and 20 g. of concentrated sulfuric acid was stirredat 70 C. for 11 hours. After standing overnight, 40 g. of sodium acetatewas added and most of the excess isobutyric acid was distilled off at 20mm. to a pot temperature of 80 C. An equal volume of water was added tothe residue and the oil layer separated. The aqueous layer was extractedwith benzene and the combined organic layer washed with 5% sodiumbicarbonate solution and with water. The washed oil was rushed-over toyield 116 g. of distillate testing 72.5% as the isobutyrate ester.Fractionation yielded u,3,3-trimethyl-cyclohexane methyl isobutyrate.

B.P. 104 C./5.4 mm. n 1.4448. 20 0.9086.

It is represented by the formula:

C H-CH3 CH3 C- L-OHa EXAMPLE IX A mixture of 220 g. of dihydromyrcene,150 g. of formic acid and 15 g. of concentrated sulfuric acid wasstirred at 50-60" C. for four hours. The lower acid layer was separatedand the top layer washed neutral with water. The crude ester weighed 257g. and tested 61% as a,3,3-trimethyl cyclohexane methyl formate.

EXAMPLE X A mixture of 200 g. of 90% formic acid, 30 g. of 85%phosphoric acid and 160 g. of dihydromyrcene was refluxed for 2.5 hours.After cooling, an equal volume of water was added and the mixtureseparated. The aqueous layer was extracted with benzene, the combinedorganic layers washed neutral with water, and the solvent stripped off.

The residue weighed 173 g. and tested 58% as 01,3,3- trimethylcyclohexane and methyl formate.

EXAMPLE XI An armoise perfume composition is prepared by mixing thefollowing ingredients in the amounts indicated.

Ingredient: Parts Cedar leaf oil 30 Sage dalmation oil 20 Peppermintnatural oil 5 Spruce oil 10 Lavender spike 5 3,3-dimethyl cyclohexylmethylketone 50 Menthone 5 EXAMPLE XII A Siberian pine needle perfumecomposition is prepared by admixing the following ingredients in theamounts indicated.

Ingredient: Parts a,3,3-trimethyl cyclohexane methyl acetate 500 Orangeoil, Florida cold pressed 300 Laurie aldehyde 3 Anethole 30 p-Hydroxybenzyl acetone 10 6 oxa 1,1,2,3,3,8 hexamethyl-2,3,5,6,7,8

hexahydro-1H-benz[f]-indene (50%) 5 7 EXAMPLE XIII A pine-like perfumecomposition is prepared by mixing the following ingredients in theproportions given.

Mousse nova trigreen p-Hydroxy benzyl acetone 3.5

1,640.0 EXAMPLE XIV A total of 100 g. of soap chips (from a toilet soapprepared from tallow and coconut oil) is mixed with one gram of theperfume composition of any of the Examples XI-XHI until a homogenouscomposition is obtained. The soap composition manifest a piney mintyodor.

EXAMPLE XV A cosmetic powder is prepared by mixing 100 g. of talcumpowder with 0.25 g. of 01,3,3-trimethyl-cyc1ohexane methyl acetate in aball mill. The cosmetic powder so 3 prepared has a desirable woodyfloral odor.

EXAMPLE XVI Concentrated liquid detergents with a piney-minty odor isprepared containing 0.1%, 0.15%, and 0.20% of the a,3,3-trimethylcyclohexane compounds of any of Examples I, III, IV, V and VIII. Theyare prepared by adding and homogeneously mixing the appropriate quantity8 of the compound to Utra Blend liquid detergent manufactured by WitcoChemical Co.

What is claimed is: 1. A perfume composition comprising a fragranceimparting amount of a compound selected from the group consisting ofcompounds having the formulas where R is an acyl group containing nomore than 4 carbon atoms as an active fragrance ingredient and anauxiliary perfume adjuvant.

2. A perfume composition as defined in claim 1 wherein said activefragrance ingredient is 3,3-dirnethyl cyclohexyl methyl ketone.

3. A perfume composition as defined in claim 1 wherein said activefragrance ingredient is a,3,3-trimethyl cyclohexane methyl formate.

' 4. A perfume composition as defined in claim 1. where in said activefragrance ingredient is a,3,3-trimethyl cyclohexane methyl acetate.'

5. A perfume composition as defined in claim 1 wherein said activefragrance ingredient is u,3,3-trimethyl cyclohexane methyl isobutyrate.

References Cited UNITED STATES PATENTS 2/1948 Morris 252-522 UX 7/1947Aeschbach 252522 UX OTHER REFERENCES ALBERT T. MEYERS, Primary ExaminerN. A. DREZIN, Assistant Examiner

1. A PERFUME COMPOSITION COMPRISING A FRAGNANCE IMPARTING AMOUNT OF ACOMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THEFORMULAS